JP2013194126A - Active energy ray-curable composition, cured product, and image display device using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active energy-ray curable composition, in which, even when a part of the active energy ray-curable composition applied to a substrate or stuck to another substrate is light-blocked, the light-blocked portion can be cured in a wide range only by application of active energy ray to an exposed portion thereof; a cured product thereof; and an image display device including a portion bonded by the active energy-curable composition.SOLUTION: An active energy ray-curable composition contains: a polymerizable compound having a carbon-carbon double bond (A); a photoradical initiator (B); a photocation generator (C); a peroxide (D); and a compound having at least three mercapto groups (E).

Description

  In the present invention, even if a part of the active energy ray-curable composition applied to the base material or bonded to another base material is shielded from light, the light-shielding portion can be cured in a wide range only by irradiating the exposed portion with the active energy ray. The present invention relates to an active energy ray-curable composition, a cured product, and an image display device bonded with the active energy ray-curable composition.

  Touch panel type displays such as smartphones, mobile terminals, tablet terminals, flat display TVs, for the purpose of improving visibility, impact resistance, durability, between the front cover board and the module, between the cover board and the touch panel, or with the touch panel A method of filling and curing between modules with a liquid resin has been proposed. In recent years, it has become possible to use a reactive adhesive that develops an adhesive property by applying an active energy ray or heat to a liquid or semi-liquid reactive oligomer or resin in the pasting process. It is advantageous in terms of fast curability. On the other hand, the cover boards of these displays may be provided with a black matrix around the cover board for various purposes such as improving image contrast, concealing IC circuits, and improving design. As described above, when a part of the active energy ray-curable material is shielded from light when the material is cured by the active energy ray irradiation, the light-shielded part is conventionally sufficient only by the active energy ray irradiation from the viewing side. There were problems in product reliability such as peeling of uncured parts, leakage of uncured components and odors, and contamination of the display part due to penetration of uncured components into the gaps between modules.

  As a method for curing the light-shielded portion, for example, in Patent Document 1, a radical curable composition is irradiated with active energy rays and then completely cured by heat, or in Patent Document 2, a moisture-reactive functional group is formed. Although the method of coexisting the polymer which has has been proposed etc., the time required for dark part curing is long, the former is damage to the substrate due to heat, the latter is the problem such as curing unevenness derived from two kinds of curing methods was there.

  Further, in Patent Document 3, an ultraviolet curable liquid material is sandwiched between a cover board having an ultraviolet non-transmissive region on the outer edge and a liquid crystal module, irradiated with ultraviolet light from the viewing side of the cover board, and then irradiated from the side surface to cure the ultraviolet non-transmissive part. Although a method has been proposed, since the configuration of the irradiation apparatus becomes complicated in order to perform side irradiation, further improvement has been demanded.

JP 2009-186957 A JP 2010-248347 A JP 2009-86656 A

  In the present invention, even if a part of the active energy ray-curable composition applied to the base material or bonded to another base material is shielded from light, only the active energy ray is irradiated to the exposed portion, and the light shielding is adjacent to the exposed portion. It is an object of the present invention to provide an active energy ray-curable composition capable of rapidly curing a part in a wide range, and a cured product, and further an image display device bonded with the active energy ray-curable composition.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have the following (A) to (E) curable compositions containing all of the components, only by irradiating the exposed portion with active energy rays. The inventors have found that the light-shielding portion adjacent to the exposed portion can also be quickly cured, and completed the present invention.

That is, the present invention
Compound (A) having polymerizable carbon-carbon double bond, photoradical initiator (B), photocation generator (C), peroxide (D), and compound having at least three mercapto groups ( It relates to an active energy ray-curable composition containing E).

  The component (A) is preferably a polymer or oligomer, and more preferably a vinyl polymer.

  (A) Component vinyl polymer is polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic acid monomer, acrylonitrile monomer, aromatic vinyl monomer, fluorine-containing vinyl monomer and silicon-containing vinyl It is preferable to select at least one polymer selected from polymers produced mainly by polymerizing monomers selected from the group consisting of system monomers.

It is preferable that the polymerizable carbon-carbon double bond at the molecular terminal in the component (A) is represented by the general formula (1).
-Z-C (= O) -C (R 1) = CH 2 (1)
(In the formula, R ¹ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, Z is a hetero atom, NR ² (R ² is a hydrogen atom, or a substituted or unsubstituted atom) A hydrocarbon group having 1 to 20 carbon atoms).

(C) component is [(R ³ ) _a (R ⁴ ) _b (R ⁵ ) _c (R ⁶ ) _d W] ^{u +} (X) ^u− (W is the formula for W, N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, I, Ti, Zr, Hf, Fe, Ru, Os, and R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different organic groups A, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. X is represented by a halogen element or [MZ _{(v + u)} ]. An inorganic or organic acid counter-base or complex, M is an element constituting the central atom of the acid counter-base or complex, O, S, Se, Te, C, Si, Ge, Sn, N, P, As, Sb, Bi, B, Al, Ga, In, Tl, Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mn, Fe, Co. Z. Is a substituent on M, or a ligand coordinated to M, and is a halogen atom or an organic group, u is a halogen element, a base of the acid, or a net charge of a complex ion, and v is M. Is preferred.).

  The component (D) is preferably an organic peroxide, and more preferably diacyl peroxide.

  Component (B) is added in an amount of 0.025 to 2 parts by weight per 100 parts by weight of component (A), and component (C) is added in an amount of 0.005 parts by weight per 100 parts by weight of component (A). 25 parts by weight to 4 parts by weight, the amount of component (D) added is 0.5 parts by weight to 3 parts by weight with respect to 100 parts by weight of component (A), and the amount of component (E) added is The amount is preferably 0.25 to 2 parts by weight with respect to 100 parts by weight of the polymer (A).

  The present invention relates to a cured product obtained by irradiating the active energy ray-curable composition with active energy rays.

  The present invention relates to an image display device produced by applying and bonding the above active energy ray-curable composition between a cover board / display module or between a cover board / display module with a touch sensor.

  The present invention relates to an electric / electronic product equipped with the image display device.

  According to the present invention, the radical generated in the curable composition is propagated in a chain manner only by irradiating the exposed portion with active energy rays, whereby the curability of the dark portion can be improved. As a result, leakage and unpleasant odor of uncured resin from the light-shielding part can be suppressed, leading to an improvement in the reliability of products containing cured products. The curable composition of the present invention is useful as an active energy ray curable adhesive, and particularly when used as a curable composition for filling between a flat panel display display module and a cover board, irradiation from the viewing side of the cover board. Thus, since the back surface of the black matrix, which is the light shielding portion, can be quickly cured, the effects of the present invention can be exhibited to the maximum.

Double Y pattern diagram Cross-sectional view of bonding of cover glass and soda glass Cross-sectional view of bonding of cover glass and LCD (liquid crystal display)

  The present invention relates to a compound (A) having a polymerizable carbon-carbon double bond, a photo radical initiator (B), a photo cation generator (C), a peroxide (D), and a mercapto group. This is an active energy ray-curable composition containing a compound (E) having two.

  The present invention will be described in detail below.

<(A) component>
The curable composition of this invention contains the compound (A) which has a polymerizable carbon-carbon double bond.

  The component (A) may contain any of a low molecular weight compound, an oligomer, and a polymer, but preferably contains a polymer or an oligomer. The oligomer described here refers to a compound having a repeating unit of an organic compound and comprising 2 to 100 repeating units, and the polymer is a structure having a repeating unit of the compound in the polymer main chain and having a structure of 100 or more. The compound which consists of a repeating unit of. The main chain of the polymer is not particularly limited, but a vinyl polymer is preferable. Examples of the polymer other than the vinyl polymer include polycarbonate, polyester, polyamide, polyoxyalkylene, and polysiloxane.

  Examples of the vinyl polymer include hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, and fluorine-containing vinyls. A polymer produced mainly by polymerizing a monomer selected from the group consisting of a system monomer and a silicon-containing vinyl monomer is preferred. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more. Furthermore, as the vinyl polymer, a (meth) acrylic polymer produced by mainly polymerizing polyisobutylene and a (meth) acrylic monomer is preferable, and a (meth) acrylic polymer is more preferable. As the (meth) acrylic polymer, an acrylic polymer is preferable, and an acrylic ester polymer produced by mainly polymerizing an acrylic ester monomer is more preferable.

  Examples of the (meth) acrylic monomer include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. N-butyl acid, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic N-heptyl acid, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate , Toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid-2-methoxy Ethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic 2-aminoethyl acid, γ- (methacryloyloxy) propyltrimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (Meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (Meth) acrylic acid diperfluoromethyl methyl, ( (Meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2-perfluoro (Meth) acrylic acid ester monomers such as hexadecylethyl; and the like.

  Examples of acrylonitrile monomers include acrylonitrile and methacrylonitrile.

  Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof.

  Examples of the fluorine-containing vinyl monomer include perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  Examples of the silicon-containing vinyl monomer include vinyltrimethoxysilane and vinyltriethoxysilane.

  Other monomers constituting the vinyl polymer include maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide , Maleimide monomers such as propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, iso Conjugated dienes such as Ren, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

  In the case where the component (A) is an oligomer or a polymer, the molecular weight distribution (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited. , Preferably less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, most preferably 1.3 or less. .

  In the GPC measurement in the present invention, a polystyrene gel column is usually used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene.

  When the component (A) is an oligomer or a polymer, the lower limit of the number average molecular weight is preferably 500, more preferably 3,000, and the upper limit is preferably 100,000, more preferably 40,000. When the molecular weight is less than 500, the original characteristics of the polymer tend to be hardly expressed, and when it exceeds 100,000, handling tends to be difficult.

The compound (A) is a compound having at least one polymerizable carbon-carbon double bond, but preferably has at least one substituent represented by the general formula (1) from the viewpoint of reactivity.
-Z-C (= O) -C (R 1) = CH 2 (1)
(In the formula, R ¹ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, Z is a hetero atom, NR ² (R ² is a hydrogen atom, or a substituted or unsubstituted atom) A hydrocarbon group having 1 to 20 carbon atoms).

  Furthermore, it is preferable that the said substituent has at a molecular terminal, and it is more preferable to have only at the terminal.

R ¹ in the general formula (1) represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. As used herein, a substituted hydrocarbon group refers to a group in which a hydrogen atom on a hydrocarbon group is substituted with a group having a hetero atom. R ¹ is not particularly limited, and examples thereof include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. In these, a hydrogen atom or a methyl group is preferable from the availability of a raw material, and also a hydrogen atom is more preferable from the high polymerization reactivity.

Z in the general formula (1) is not particularly limited, and examples thereof include an oxygen atom; a sulfur atom; and an amino group such as —NH— and —NCH ₃ —. In these, an oxygen atom and -NH- group are preferable from the ease of introduction | transduction, and an oxygen atom is more preferable.

  The number of substituents represented by the general formula (1) is not particularly limited, but when the component (A) is an oligomer or a polymer, the average number is less than 1 per molecule from the viewpoint that the compounds (A) are cross-linked. Since there exists a tendency for sclerosis | hardenability to become low, one or more is preferable on average. However, in order to adjust the hardness and flexibility of the cured product with respect to the compound (A) having one or more substituents represented by the general formula (1) on average per molecule, the average is less than 1 per molecule An organic polymer having a substituent represented by the general formula (1) may be added. In addition, the substituent represented by the general formula (1) may be present in either the side chain and / or the terminal of the molecule, but the molecular weight between the crosslinking points is uniform and large (preferably 500 to 100,000). From the viewpoint of obtaining good rubber elasticity, it is preferable to exist at the end of the molecule, and more preferable to exist only at the end of the molecule.

  The low molecular weight compound may be any as long as it has a polymerizable carbon-carbon double bond, but preferably has one or more substituents represented by the general formula (1). More preferably, it is a (meth) acrylic monomer.

<Production method of component (A)>
Although there is no limitation in particular about the manufacturing method of (A) component, when (A) component is a vinyl polymer, it is generally manufactured by anionic polymerization or radical polymerization. Of these, radical polymerization is preferred because of the versatility of the monomer and ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

  The radical polymerization method used for the production of the component (A) is a method in which an azo compound or peroxide is used as a polymerization initiator, and a monomer having a specific functional group and a vinyl monomer are simply copolymerized. Can be classified into “radical polymerization methods” and “controlled radical polymerization methods” in which specific functional groups can be introduced at controlled positions such as terminals.

  The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount, and conversely, in the case of using a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

  The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal without causing a termination reaction or the like.

  In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

  Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  Therefore, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The production method of the vinyl polymer having the specific functional group is more preferable.

  In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years.
Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, “Atom transfer radical polymerization” using radical scavengers such as nitroxide compounds as shown in Macromolecules, 1994, 27, 7228, organic halides as initiators and transition metal complexes as catalysts. (Atom Transfer Radical Polymerization: ATRP).

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts. Therefore, production of vinyl polymers having specific functional groups The method is more preferable.

  Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421 pamphlet, WO97 / 18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, And the method described on page 1721.

  In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the standpoint of ease of control, and particularly an atom. The transfer radical polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method of obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

  Next, a more preferred atom transfer radical polymerization method among living radical polymerization methods will be described. In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen Sulfonyl compounds and the like are used as initiators.

If Specific _{examples, C 6 H 5 -CH 2 X} , C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom)
^{R 7 -C (H) (X} ) -CO 2 R 8, R 7 -C (CH 3) (X) -CO 2 R 8, R 7 -C (H) (X) -C (O) R 8 R ⁷ —C (CH ₃ ) (X) —C (O) R ⁸ ,
Wherein R ⁷ and R ⁸ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom )
R ⁷ —C ₆ H ₄ —SO ₂ X
(Wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

  In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.

  There is no restriction | limiting in particular in the vinyl-type monomer used in the said superposition | polymerization, and all already illustrated can be used suitably.

  Further, the transition metal complex used as the polymerization catalyst is not particularly limited, but preferably a metal complex having a group 7 element, group 8, group 9, group 10 or group 11 element as a central metal, such as copper, It is a complex of nickel, ruthenium and iron. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable.

  Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. Can be given.

  In the case of using a copper compound, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. to increase the catalytic activity A ligand such as a polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.

  When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.

Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.
Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.

  Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

  There are no particular limitations on the method for introducing the functional group of the component (A). For example, a vinyl polymer having a reactive functional group is produced by the method described above, and the reactive functional group is substituted with a (meth) acryloyl group. It can manufacture by converting into a group.

  Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

  The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.

(Introduction Method 1) A method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
M ⁺ —OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
As the vinyl polymer having a halogen group at the terminal, one having a terminal group represented by the general formula (3) is preferable.
-CR ⁹ R ¹⁰ X (3)
(Wherein R ⁹ and R ¹⁰ are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, bromine atom or iodine atom)
(Introduction method 2) A method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
(Introduction method 3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group reacts with the compound represented by the general formula (5).
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
Below, each said method is demonstrated in detail.

[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).

  Although there is no limitation in particular in the vinyl polymer which has a halogen group at the terminal, What has a terminal group shown in General formula (3) is preferable.

  A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-described organic halide or sulfonyl halide compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

  There is no limitation in particular in the compound represented by General formula (2).

Examples of the organic group having 1 to 20 carbon atoms in ^Ra in the general formula (2) are the same as those described above, and specific examples thereof are also the same as those described above.

M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples thereof include alkali metal ions and quaternary ammonium ions.

  Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, and tetrabutyl. Examples thereof include ammonium ion and dimethylpiperidinium ion. Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

  The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.

  The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.

  Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).

Examples of the organic group having 1 to 20 carbon atoms in ^Ra in General Formula (4) are the same as those described above, and specific examples thereof are also the same as those described above.

  The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Although it is produced by a method of polymerizing a vinyl monomer, the former is preferred.

  Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following methods are illustrated.

(A) A method of reacting, as a second monomer, a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the general formula (6) when a vinyl polymer is synthesized by living radical polymerization .
^{_{H 2 C = C (R 11}} ) -R 12 -R 13 -OH (6)
(Wherein R ¹¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹² is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹³ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
R ¹¹ is preferably a hydrogen atom or a methyl group. Further, when R ¹² is an ester group, it is a (meth) acrylate compound, and when R ¹² is a phenylene group, it is a styrene compound.
There is no restriction on the timing for reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (7).
^{_{H 2 C = C (R 11}} ) -R 14 -OH (7)
(In the formula, R ¹¹ is the same as described above, and R ¹⁴ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
The compound represented by the general formula (7) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

  (C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolyzing or reacting a halogen atom with a hydroxyl group-containing compound.

(D) A vinyl-based polymer having at least one carbon-halogen bond represented by general formula (3) obtained by atom transfer radical polymerization is reacted with a stabilized carbanion having a hydroxyl group represented by general formula (8). To replace the halogen.
M ^<+>- C- (R ^{< 15 >} ) (R ^{< 16 >} )-R ^{< 14 >} -OH (8)
(Wherein R ¹⁴ and M ⁺ are the same as described above, R ¹⁵ and R ¹⁶ are both electron-withdrawing groups for stabilizing carbanion C— or one of them is the electron-withdrawing group, the other is a hydrogen atom, and has 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group of
As the electron-withdrawing group, -CO ₂ R (ester group), - C (O) R ( keto ^{group), - CON (R 2)} ( amide group), - COSR (thioester group), - CN (nitrile group ), —NO ₂ (nitro group) and the like, and —CO ₂ R, —C (O) R, and —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

  (E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) a vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a hydroxyl group-containing compound represented by the general formula (9),
HO-R ¹⁴ -OM ⁺ (9)
(Wherein R ¹⁴ and M ⁺ are the same as above)
A method of reacting the hydroxyl group-containing compound represented by the general formula (10) and replacing the halogen atom with a hydroxyl group-containing substituent.
^{HO-R 14 -C (O)} O-M + (10)
(Wherein R ¹⁴ and M ⁺ are the same as above)

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

  The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.

  The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.

  Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
Introducing method 3 is a method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group reacts with the compound represented by formula (5).
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
Examples of the organic group having 1 to 20 carbon atoms in ^Ra in General Formula (5) are the same as those described above, and specific examples thereof are also the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And alkylene groups having 7 to 20 carbon atoms.

The compound represented by the general formula (5) is not particularly limited, and particularly preferable compounds include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

  There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Examples thereof include xylylene diisocyanate and isophorone diisocyanate. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining superior weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

  The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.

  The reaction solvent is not particularly limited, but an aprotic solvent is preferred.

  Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

  The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.

<(B) component>
Although it does not specifically limit as radical photopolymerization initiator (B) contained in the curable composition of this invention, For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophene, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro Rho-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane 1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho And linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like. Among these, phenyl ketone compounds are preferred in that they have tack-improving properties.

  In addition, an acylphosphine oxide photopolymerization initiator having excellent deep curability during UV irradiation can also be blended. Acylphosphine oxide polymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -isobutylphosphine oxide, bis (2 , 6-dimethoxybenzoyl) -isobutylphosphine oxide, bis (2,6-dimethoxybenzoyl) -phenylphosphine oxide, etc., preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl - a pentyl phosphine oxide. The above photo radical initiators may be used alone or in combination of two or more.

  In the curable composition of the present invention, the acylphosphine oxide and the phenyl ketone compound can be used in combination.

  The addition amount of the photo radical initiator (B) is preferably 0.025 parts by weight to 2 parts by weight, and 0.05 parts by weight to 1 part by weight with respect to 100 parts by weight of the component (A). preferable. When the amount is less than 0.025 parts by weight, the dark portion curability is not exhibited, and the curability of the irradiated portion is not sufficient. If it is more than 2 parts by weight, the physical properties of the cured product may be affected.

<(C) component>
The photocationic initiator (C) contained in the curable composition of the present invention contains [(R ³ ) _a (R ⁴ ) _b (R ⁵ ) _c (R ⁶ ) _d W] ^{u +} (X) ^u− (formula W is N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, I, Ti, Zr, Hf, Fe, Ru, Os, and R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different organic groups, a, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. X is a halogen element Or an inorganic or organic acid counter-base or complex represented by [MZ (v + u)], where M is an element constituting the central atom of the acid counter-base or complex, and is O, S, Se, Te C, Si, Ge, Sn, N, P, As, Sb, Bi, B, Al, Ga, In, Tl, Ti, Zr, Hf, Sc, , Nb, Ta, Cr, Mn, Fe, Co. Z is a substituent on M or a ligand coordinated to M, and is a halogen atom or an organic group, u is a halogen element, It is preferably the net charge of the base or complex ion, v is the valence of M). Among them, W is S, I, R ³ , R ⁴ , R ⁵ , and R ⁶ are substituted or unsubstituted phenyl groups, X is tetraphenyl borate, tetrafluoroborate, hexafluorophosphate, Those that are hexafluoroantimonates are preferable in terms of availability.

  Specifically, diphenyliodonium-hexafluorophosphate, bis (p-alkylphenyl) iodonium-hexafluorophosphate, bis (p-alkylphenyl) iodonium-hexafluoroantimonate, triphenylsulfonium-hexafluorophosphate, Examples include tris (p-alkylphenyl) sulfonium-hexafluorophosphate and tris (p-alkylphenyl) sulfonium-hexafluoroantimonate. These photo cation generators may contain a solvent.

  The addition amount of the photocation generator (C) is preferably 0.25 to 4 parts by weight, and 0.5 to 3 parts by weight with respect to 100 parts by weight of the component (A). preferable. When the amount is less than 0.25 parts by weight, the dark portion curability is not exhibited, and when the amount is more than 4 parts by weight, the physical properties of the cured product may be affected.

<(D) component>
The peroxide contained in the curable composition of the present invention is preferably an organic peroxide in terms of stability and compatibility. Examples of the organic oxide include hydroperoxide, dialkyl peroxide, peroxycarbonate, peroxycarboxylic acid, and esters thereof, diacyl peroxide, and the like. Among these, diacyl peroxide is preferable in terms of dark part curability during the reaction. Examples of the diacyl peroxide include benzoyl peroxide, toluyl peroxide, acetyl peroxide, and lauroyl peroxide. These peroxides may contain solvents such as toluene, xylene and water.

  The amount of the peroxide (D) added is preferably 0.5 to 3 parts by weight, and preferably 1 to 2 parts by weight with respect to 100 parts by weight of the component (A). When the amount is less than 0.5 part by weight, the dark portion curability is not exhibited, and when the amount is more than 3 parts by weight, the storage stability of the curable composition is deteriorated.

<(E) component>
In the present invention, it was found that dark portion rapid curing can be achieved by adding a compound (E) having at least three mercapto groups in addition to the components (A) to (D). As the component (E), trimethylolpropane (tris) (2-mercaptopropionate), tris- (3-mercaptopropionyloxy) -ethyl) -isocyanurate, pentaerythritol (tetrakis) (2-mercaptopropionate) ), Bis (pentaerythritol) (hexakis) (2-mercaptopropionate), and the like.

  The amount of component (E) added is preferably 0.25 to 2 parts by weight, and preferably 0.5 to 1 part by weight per 100 parts by weight of component (A). When the amount is less than 0.25 parts by weight, the dark portion curability is not exhibited, and when the amount is more than 2 parts by weight, the physical properties of the cured product may be affected.

<Other additives>
The curable composition of the present invention contains other components such as a radical scavenger, a plasticizer, a silane coupling agent, a filler, a modifier, and other resin components as long as the effects of the present invention are not impaired. can do. The radical scavenger mentioned here generally includes what are called antioxidants and light stabilizers. The antioxidant is not particularly limited, and examples thereof include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Among these, hindered phenol-based antioxidants are preferable. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF Corporation); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (above, All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all are manufactured by Sankyo Co., Ltd.) The indicated hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). It is. If the amount used is smaller than this, sufficient effects may not be obtained. If the amount used is larger than this, it is not only economically disadvantageous, but also radicals generated from the photo radical initiator. May be captured by an antioxidant, resulting in poor curing of the cured product, and the cured product may not exhibit good physical properties.

  Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds. Among these, hindered amine compounds are preferable. The light stabilizer is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). If the amount used is smaller than this, sufficient effects may not be obtained. If the amount used is larger than this, it may not only be economically disadvantageous, but also a photo radical initiator. There is a possibility that the antioxidant is supplemented by the generated radicals, and the cured product is poorly cured, and the cured product does not exhibit good physical properties. Specific examples of the light stabilizer are also shown in JP-A-9-194731.

  Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate and dioctyl sebacate; diethylene glycol dibenzoate Polyalkylene glycol esters such as triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl alone , Or a mixture of two or more types, but is not necessarily required. In addition, these plasticizers can also be mix | blended at the time of saturated hydrocarbon type polymer manufacture. The amount of the plasticizer used is preferably in the range of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, relative to 100 parts by weight of component (A). When the amount used is less than this, a sufficient effect may not be obtained, and when the amount used is larger than this, the mechanical properties of the obtained cured product may be lowered. The addition of a plasticizer is effective for adjusting physical properties and properties.

  Examples of the silane coupling agent include silane compounds having a reactive group such as an epoxy group, a carboxyl group, a methacryloyl group, and an isocyanate group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethylsilane and the like. These may be used alone or in combination of two or more. Although the content rate of the silane coupling agent component in the resin composition of this invention does not have limitation in particular, A total of 100 of (A) component, (B) component, (C) component, (D) component, (E) component It is 0.1-20 weight part normally with respect to a weight part, Preferably it is 0.3-10 weight part. Addition of a silane coupling agent is effective for improving adhesiveness and water resistance.

  Examples of the filler include fine particle silica, glass beads, talc, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles. Among them, inorganic fillers are preferable, and fine particle silica is particularly preferable. preferable. These may be used alone or in combination of two or more. Although the content rate of a filler component does not have limitation in particular, It is 20-150 weight part normally with respect to 100 weight part of (A) component, Preferably it is 50-100 weight part. By adding an inorganic filler, it is possible to improve the strength, moisture permeability resistance and adhesion.

  Examples of the modifier include polymerization initiation assistants, leveling agents, wettability improvers, surfactants, and the like. These may be used alone or in combination of two or more.

<Curable composition>
The curable composition of this invention is prepared by mixing each component uniformly. There is no particular limitation on the mixing method, but it is possible to mix the peroxide of the component (D) after thoroughly mixing the other components except the peroxide of the component (D). It is preferable in terms of safety. In the case of mixing, the apparatus is not particularly limited, but it is prepared by appropriately mixing using a hand stirring, a mechanical stirring apparatus, a roll mill or the like.

  Examples of the active energy ray for curing the curable composition of the present invention include light (UV) and electron beam, and it is preferable to cure by light (UV).

  The active energy ray source is not particularly limited, but may be, for example, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, or a metal halide depending on the nature of the photopolymerization initiator used. It is done.

  The curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.

<Coating method to image display device>
As a coating method for an image display device, there are a spray coating, a printing method such as screen printing, and a pattern coating method using a dispenser. From the viewpoint of preventing mixing of bubbles during bonding, a coating method using a dispenser is available. preferable.

  Further, the coating pattern is not particularly limited, and examples thereof include full-surface coating, a linear pattern, a comb pattern, a circular pattern, a double Y-shaped pattern (FIG. 1), and a snow-shaped pattern.

  The curable composition in the present invention is useful as an adhesive, a paint, a sealing agent composition, a waterproofing agent, a spraying agent, a molding material, an injection rubber material, and the like. Specifically, UV curable materials, coatings, inks, liquid solder resists, liquid crystal resists, optical fiber coating agents, UV / visible light curable adhesives, optical disk coating agents, electronic component sealants, image display devices Visibility improvers and the like can be mentioned, but from the viewpoint of dark portion rapid curing by irradiation with active energy rays, the effect of the present invention is exhibited particularly in applications as a visibility improver filled between the image display device and the cover board. can do.

  The module to be bonded is not particularly limited, but a liquid crystal module, a touch sensor using the same, a plasma display panel, an E-ink type display module for electronic paper, a SIPIX type display module, an organic EL, etc. A display module is mentioned.

  Further, the parts to be bonded are between the touch sensor and the display module, between the cover board and the display module, between the cover board and the touch sensor, or between the cover board with the touch sensor and the display module. In particular, since the black matrix is often applied to the cover board side, the effect of the present invention is maximized in the bonding between the cover board and the display module or between the cover board with the touch sensor and the display module. Can do.

  In addition, after bonding between the cover board / display module and between the cover board / display module with touch sensor, until the liquid resin is sufficiently leveled, It is preferable to temporarily fix a part. As a temporary fixing method, UV irradiation is preferable in that only a part can be fixed.

<Application>
As electric / electronic products equipped with a display device bonded with a curable composition of the present invention, portable electronic terminals such as TVs, mobile phones, smartphones, portable media players, PDAs, digital cameras, personal computers, Electronic paper, car navigation systems, in-vehicle display meters, refrigerators equipped with display devices, microwave ovens, household appliances such as washing machines, game machines, slot machines, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.

  In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, LC Module 1 manufactured by Waters was used as the GPC system, polystyrene crosslinked gel was used as the GPC column (Shodex GPC K-804; manufactured by Showa Denko KK), and chloroform was used as the GPC solvent.

The “average terminal (meth) acryloyl group number” is “the number of (meth) acryloyl groups introduced per polymer molecule”, and was calculated from the number average molecular weight determined by ¹ H-NMR analysis and GPC. (However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.)

(Production Example 1)
(1) Polymerization process n-butyl acrylate was deoxygenated. The inside of the stainless steel reaction vessel with a stirrer was deoxygenated, and cuprous bromide and a part of all n-butyl acrylate (described as initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1), diethyl 2,5-dibromoadipate (DBAE) as an initiator were added and mixed, and at the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter, (Abbreviated as triamine) was added to initiate the polymerization reaction. The remaining n-butyl acrylate (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(3) First crude purification Butyl acetate was used as a diluent solvent for the polymer. Dilute the concentrate of (2) with about 100-150 kg of butyl acetate per 100 kg of polymer, and add a filter aid (Radiolite R900, Showa Chemical Industry Co., Ltd.) and an adsorbent (Kyoward 700 SEN, Kyoward 500 SH). Added. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.
(4) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAc), potassium acrylate (about 2 molar equivalents relative to terminal Br group), heat stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. A polymer [P1] having Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
As the component (A) described in Production Example 1, 100 parts by weight of a polymer [P1] having an acryloyl group at the terminal and 30 parts by weight of lauryl acrylate (Light Eryacrylate LA, manufactured by Kyoeisha Chemical Industry Co., Ltd.) In addition to the cup, as component (B), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF DAROCURE 1173) 0.8 part by weight, (2,4,6-trimethylbenzoyl)- Diphenyl phosphine oxide (LUSFIRIN TPO, manufactured by BASF) 0.1 parts by weight, (C) component, bis (p-alkylphenyl) iodonium-hexafluorophosphate / 50% propylene carbonate solution (Wako Pure Chemical Industries, Ltd.) WPI-113) 3 parts by weight, as component (E), pentaerythritol (tetrakis) (3-me (Captopropionate) (PEMP manufactured by SC Organic Chemistry Co., Ltd.) 0.5 parts by weight was added and mixed with a spatula with sufficient agitation. Substituted benzoyl peroxide 40% p- as component (D) A curable composition was obtained by adding 4 parts by weight of a xylene solution (Niper BMT manufactured by NOF Corporation) and stirring and mixing.

A predetermined amount of the curable composition is set in FIG. 1 so that the film thickness becomes 0.2 mm on a 0.7 mm thick glass cover glass having a black matrix having a width of 2.0 cm and a thickness of 0.05 mm. After dispensing the pattern shown, it was bonded to 0.7 mm thick soda glass, and the side surfaces were shielded with aluminum tape so as not to irradiate the bonded side surfaces with UV (FIG. 2). Irradiation was performed with a UV irradiation apparatus (model: LIGHT HAMMER 6, light source: mercury lamp lamp, peak illuminance 600 mW / cm ² ) (integrated light amount: 6000 mJ / cm ² ) manufactured by Fusion UV System, and a bonded cured product was obtained.

  After UV irradiation, naturally cool for 1 minute at room temperature, insert a spatula between the coverboard / soda glass of the resulting bonded cured product, slowly peel off the coverboard, And the width | variety which the curable composition of the part which hits a black matrix back | cured was measured (FIG. 2). The curability was determined by palpating the curable composition after UV irradiation, and when the curable composition did not flow or migrate and had elasticity. The cured width is shown in Table 2.

(Examples 2-7, Comparative Examples 1-10)
In the same process as in Example 1, the components shown in Tables 2 and 3 were blended to obtain a curable composition. Subsequently, a bonded cured product was obtained in the same manner, and the cured width of the back of the black matrix was measured. Details of each formulation and the cured width are shown in Tables 2 and 3.

The abbreviations in Tables 2 and 3 are as follows.
LA: Lauryl acrylate (Kyoeisha Chemical Co., Ltd. light acrylate LA)
DAROCUR1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF)
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF)
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF)
TPO: (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide (LUCIRIN TPO manufactured by BASF)
WPI-113: Bis (p-alkylphenyl) iodonium-hexafluorophosphate, 50% propylene carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.)
BMT: Benzoyl peroxide / toluyl peroxide mixture, 40% p-xylene solution (Niper BMT manufactured by NOF Corporation)
PEMP: Pentaerythritol (tetrakis) mercaptopropionate (manufactured by SC Organic Chemical Co., Ltd.)
TMMP: Trimethylolpropane (Tris) (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.)
DPMP: Dipentaerythritol (hexakis) (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.)
EGMP-4: Tetraethylene glycol (bis) (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.)
ESC: Ethanesulfonyl chloride (Wako Pure Chemical Industries, Ltd.)
DPDS: Diphenyl disulfide (Wako Pure Chemical Industries, Ltd.)

  In Examples 1 to 7 using the compound (E) containing three or more mercapto groups, the dark portion has a longer cured width than that of Comparative Examples 1 to 10, and the dark portion curability is improved. Compared with the curable composition used in Example 1, among (B) component, (C) component, (D) component, and (E) component, only the (B) component photoradical initiator is included ( Comparative Example 1), (B) component not containing a photoradical initiator (Comparative Example 2), (C) component not containing a photocation generator (Comparative Example 3), (D) component peroxidation In the case where no product was added (Comparative Example 4) and the case where the compound having a mercapto group as the component (E) was not added (Comparative Example 5), the curability of the dark part did not reach Example 1 in any combination. In Comparative Example 2, the curability of the exposed area was poor. Instead of pentaerythritol (tetrakis) (3-mercaptopropionate) described in Example 1, tetraethylene glycol (bis) (3-mercaptopropionate) having 2 mercapto groups was added to each of 0. When 5 parts, 1 part, or 2 parts was added, the curability of the dark part did not reach Example 1 in any case (Comparative Examples 6 to 8). When other chain transfer agents having no mercapto group were used, dark part curability was not exhibited (Comparative Examples 9 and 10).

(Example 8)
A predetermined amount of the curable composition obtained in Example 1 is applied to a cover glass having a black matrix having a width of 5 mm so as to have a film thickness of 200 μm. After dispensing in the pattern shown in FIG. Irradiation was performed with a UV irradiation apparatus (model: LIGHT HAMMER 6, light source: mercury lamp, integrated light quantity: 6000 mJ / cm ² ) manufactured by UV system, and an image display apparatus having the structure shown in FIG. 3 was obtained.
Table 3 shows the display performance of the obtained image display device after the heat shock 500 cycle test.

(Comparative Example 11)
A predetermined amount of the curable composition obtained in Comparative Example 1 is applied to a cover glass having a black matrix having a width of 5 mm so as to have a film thickness of 200 μm. After dispensing the pattern shown in FIG. Irradiation was performed with a UV irradiation apparatus (model: LIGHT HAMMER 6, light source: mercury lamp, integrated light quantity: 6000 mJ / cm ² ) manufactured by UV system, and an image display apparatus having the structure shown in FIG. 3 was obtained.
Table 4 shows the display performance of the obtained image display device after the heat shock 500 cycle test.

  In the image display device of Example 8 that rapidly cures in the dark part, there was no leakage of uncured material and no odor associated therewith after the heat shock, and there was no contamination of the display part. In the image display device of Comparative Example 11, uncured material leaks and odor is generated, and the uncured material enters the inside through the gap between the LCD panel of the LCD module and the outer frame to contaminate the display portion, Could not display the whole.

1. Cover board Black matrix 3. Curable composition 4. Aluminum tape Soda glass LCD panel 7. Light reflector, diffuser plate 8. LCD module outer frame

Claims (12)

Compound (A) having polymerizable carbon-carbon double bond, photoradical initiator (B), photocation generator (C), peroxide (D), and compound having at least three mercapto groups ( An active energy ray-curable composition containing E). The active energy ray-curable composition according to claim 1, wherein the component (A) is a polymer or an oligomer. The active energy ray-curable composition according to claim 2, wherein the polymer or oligomer of the component (A) is a vinyl polymer. (A) Component vinyl polymer is polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic acid monomer, acrylonitrile monomer, aromatic vinyl monomer, fluorine-containing vinyl monomer and silicon-containing 4. The active energy ray-curable composition according to claim 3, wherein at least one polymer is selected from polymers produced mainly by polymerizing monomers selected from the group consisting of vinyl monomers. The active energy ray-curable property according to any one of claims 1 to 4, wherein a polymerizable carbon-carbon double bond at a molecular end in the component (A) is represented by the general formula (1). Composition.
-Z-C (= O) -C (R 1) = CH 2 (1)
(In the formula, R ¹ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, Z is a hetero atom, NR ² (R ² is a hydrogen atom, or a substituted or unsubstituted atom) A hydrocarbon group having 1 to 20 carbon atoms). (C) component is [(R ³ ) _a (R ⁴ ) _b (R ⁵ ) _c (R ⁶ ) _d W] ^{u +} (X) ^u− (W is the formula for W, N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, I, Ti, Zr, Hf, Fe, Ru, Os, and R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different organic groups. A, b, c, and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. X is a halogen element or an inorganic material represented by [MZ _{(v + u)} ] Or an organic acid counter-base or complex, wherein M is an element constituting the central atom of the acid counter-base or complex, O, S, Se, Te, C, Si, Ge, Sn, N, P As, Sb, Bi, B, Al, Ga, In, Tl, Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mn, Fe, Co. Z is on M Or a ligand coordinated to M, which is a halogen atom or an organic group, u is the halogen element, the net charge of the acid counter-base or complex ion, and v is the valence of M. The active energy ray-curable composition according to any one of claims 1 to 5, wherein The active energy ray-curable composition according to claim 1, wherein the component (D) is an organic peroxide. The active energy ray-curable composition according to claim 7, wherein the organic peroxide as component (D) is diacyl peroxide. Component (B) is added in an amount of 0.025 to 2 parts by weight per 100 parts by weight of component (A), and component (C) is added in an amount of 0.005 parts by weight per 100 parts by weight of component (A). 25 parts by weight to 4 parts by weight, the amount of component (D) added is 0.5 parts by weight to 3 parts by weight with respect to 100 parts by weight of component (A), and the amount of component (E) added is The active energy ray-curable composition according to any one of claims 1 to 8, wherein the content is from 0.25 to 2 parts by weight based on 100 parts by weight of the polymer (A). A cured product obtained by irradiating the active energy ray-curable composition according to claim 1 with active energy rays. An image display device produced by applying and bonding the active energy ray-curable composition according to any one of claims 1 to 9 between a cover board / display module or between a cover board / display module with a touch sensor. An electrical / electronic product equipped with the image display device according to claim 11.

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